CN101380568A - Composite metal ion doped with TiO2 photocatalyst transparent emulsion and preparation method thereof - Google Patents
Composite metal ion doped with TiO2 photocatalyst transparent emulsion and preparation method thereof Download PDFInfo
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- CN101380568A CN101380568A CNA2008100795997A CN200810079599A CN101380568A CN 101380568 A CN101380568 A CN 101380568A CN A2008100795997 A CNA2008100795997 A CN A2008100795997A CN 200810079599 A CN200810079599 A CN 200810079599A CN 101380568 A CN101380568 A CN 101380568A
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- vanadium
- cerium
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- 239000000839 emulsion Substances 0.000 title claims abstract description 46
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 25
- 238000004945 emulsification Methods 0.000 title description 3
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 229920000136 polysorbate Polymers 0.000 claims abstract description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims abstract description 4
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000010009 beating Methods 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 abstract 1
- NWGKJDSIEKMTRX-BFWOXRRGSA-N [(2r)-2-[(3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)C1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-BFWOXRRGSA-N 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 229960002920 sorbitol Drugs 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
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- 230000007935 neutral effect Effects 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
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- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
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- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to a transparent photocatalyst emulsion of composite metal ion doped with nano TiO2, which is characterized in that the emulsion comprises the following components by weight proportion: nano TiO2, 2.1 to 20 percent of metal salt containing lanthanum, cerium and vanadium, 1 to 10 percent of tween, arlacel, D-sorbitol or OP emulsifier and the residual amount of water. The mole ratio of the metal salt containing lanthanum, cerium and vanadium and titanium is 3.0 to 10 percent. The invention adopts inorganic salts with low price of titanium tetrachloride, lanthanum nitrate, cerous sulfate and metavanadic acid, and the like, adopts low-temperature complexation-control hydrolysis reaction to prepare the transparent photocatalyst emulsion of composite metal ion doped with nano TiO2, leads the materials to form more doping levels, thus widening the response interval of spectrum; the invention has the biggest advantages that sunlight or a fluorescent light is utilized directly to realize complete degradation to the organic pollutants of formaldehyde, benzene, dye, pesticide, microorganism and the like, and the speed and efficiency of degradation of organic matter by photocatalysis is improved, thus realizing the purification to environment.
Description
Technical field
The present invention relates to a kind of composite metal ion doped nano-TiO
2Transparent photo-catalytic emulsion and preparation method belong to chemical synthesis purification techniques field.
Background technology
In recent years, a large amount of synthetic materials, automobile making material that the home dwelling finishing uses cause very big pollution sources to the human settlement, the Treatment by Photocatalysis Oxidation technology can finally be degraded to nontoxic inorganic molecules to pollutant as a kind of novel method for governing pollution, thoroughly environment purification.The Nano titanium dioxide photocatalyst of broad research is the photocatalytic-oxidation formed material that application potential is arranged in the world today most at present, can be used in to handle on the various environmental problems.But nano-titanium dioxide powder is easy to reunite in the preservation process, is difficult to reclaim in photocatalytic process, because these shortcomings have limited its practical application.Compare with conventional powder, nano titanium oxide photo-catalytic emulsion good stability in depositing process is convenient to preserve, and becomes current research focus.But the development of nano titanium oxide photo-catalytic emulsion both at home and abroad mostly is greatly with nano-titanium dioxide powder and handles the emulsion of making through special process, because of the nano-powder agglomeration serious, disperse difficulty very big again, power consumption is high, so the emulsion dispersion of this technology preparation is poor, stability is bad.The emulsion that also useful chemical method is directly synthetic, dispersed and better stable, but titanium dioxide is wide-band gap material (3.2eV), only can absorb the ultraviolet light part of solar spectrum, usually need excite with ultraviolet source, solar energy utilization ratio low (solar spectrum medium ultraviolet light less than 5%), this has limited the application of its reality.Also there is transparent photo-catalytic to enter into market such as some Japanese recently company, but is pure anatase type nano TiO
2Emulsion.Therefore, in order effectively to utilize sunshine, energy savings, exploitation can be by photochemical catalyst excited by visible light, that have highlight catalytic active, becomes one of key issue that photocatalysis technology practicability need solve just day by day.In order to improve the utilization rate of titanium dioxide to sunshine, people have carried out many good tries, wherein the most noticeablely be to use the light-sensitive coloring agent sensitization, report with organic dye sensitized titanium dioxide as people such as Ross and can improve utilization rate solar spectrum, but exist absorption competition between sensitizer and the pollutant, the titanium dioxide photostability after the sensitization simultaneously is also undesirable.People such as Falconer adopt the Pt precious metal doping to TiO
2Carried out modification, but the expensive price of noble metal is well-known; People such as Chol adopt surplus Fe, Co, the Zn etc. ten metal ion species respectively to nano-TiO
2Carried out the research of mixing, but owing to be independent metal ion mixing, the material property improvement there is no big breakthrough, in actual application, still it is slow to exist the right transfer velocity in doping few, photic electronics of energy and hole, the problem that recombination rate is high, the deficiency that causes that the photocatalysis quantum efficiency is low, photocatalytic activity is not high and be difficult to make full use of aspects such as solar energy.
Summary of the invention
The object of the present invention is to provide a kind of with common, inexpensive inorganic salts TiCl
4Be raw material, adopt the compound multiple metal ion coblended nano TiO 2 transparent photo-catalytic emulsion of low temperature complexing-control hydrolysis preparation, can fully increase doped energy-band,, improve the photocatalysis effect under solar radiation greatly to widen titanium dioxide emulsion spectral response interval.
The object of the present invention is achieved like this: this composite metal ion doped nano-TiO
2The photocatalyst transparency emulsion is characterized in that: comprise following part by weight in this emulsion: nano-TiO
2, the slaine that contains lanthanum, cerium and vanadium totally 2.1～20%, tween, class of department, D-D-sorbite or OP class emulsifying agent 1-10%, water surplus.
Described composite metal ion doped nano-TiO
2The photocatalyst transparency emulsion describedly contains the slaine of lanthanum, cerium and vanadium and the mol ratio of titanium is 3.0-10%.
Described composite metal ion doped nano-TiO
2The preparation method of photocatalyst transparency emulsion, this emulsion prepares according to following steps:
A, the composite metal ion doped titanium tetrachloride aqueous solution of preparation:
According to the mol ratio of doped metal ion and titanium is that slaine that the ratio of 3.0-10% will contain lanthanum, cerium and vanadium is dissolved in the 100mL water and makes saline solns, gets the 33mL titanium tetrachloride and slowly splashes in the saline solns with separatory funnel, and it is fully mixed;
Or: under the room temperature, will analyze pure titanium tetrachloride and slowly splash in the distilled water, and be mixed with 10～50% clear solution, be that the ratio of 3.0-10% adds the slaine that contains cerium and vanadium according to the mol ratio of doped metal ion and titanium, is stirred to whole dissolvings;
B, hydrolysis:
Get the aqueous solution of steps A, add pure water 300～2000ml again, the slow ammoniacal liquor of Dropwise 5～13% in this solution then, adjust pH is 8～9, makes TiO
2+And La
3+, Ce
3+And VO
3+Produce the composite oxides co-precipitation, then vacuum filtration, spend deionised water up to not containing Cl with the liquor argenti nitratis ophthalmicus check
-Till, obtain being mixed with the TiO of composite metal ion
2Filter cake;
C, complexing:
Above-mentioned filter cake is added 10-100 water making beating doubly, after 5～90 minutes, place round-bottomed flask with the high-speed shearing machine shearing, add the hydrogen peroxide of 10～100ml 15%, at 0～10 ℃ of stirring reaction 3-12 hour, obtain complex solution faint yellow or that yellowish-brown is transparent;
D, decomposition complex compound
Get the above-mentioned clear solution of 400ml, add D-D-sorbite, op-10 emulsifying agent, oleic acid or the tween of 0.8～10g, decompose complex compound, be mixed with the nano-TiO of the composition metal doping of lanthanum, cerium and vanadium simultaneously at 110～150 ℃ of heating, stirring and refluxing 0.5-2h
2Transparent photo-catalytic emulsion.
Described composite metal ion doped nano-TiO
2The preparation method of transparent photo-catalytic emulsion is characterized in that:step B doping adds the slaine that contains lanthanum, cerium and vanadium and comprises lanthanum nitrate and cerous sulfate and Pian Fan Suan .
Composite metal ion doped nano-TiO provided by the invention
2The technological progress effect of transparent photo-catalytic emulsion shows:
The present invention is a raw material with the titanium tetrachloride and the inorganic salts such as lanthanum nitrate and cerous sulfate and metavanadic acid of cheapness, adopt low temperature complexing-control hydrolysis to prepare and be mixed with lanthanum simultaneously, the composite mixed metal ion nano titanium oxide transparent photo-catalytic emulsion of cerium and vanadium, make material form more doped energy-band, thereby widened the spectral response interval, its sharpest edges are directly to utilize sunshine or fluorescent lamp, realize PARA FORMALDEHYDE PRILLS(91,95), the benzene class, dyestuff, agricultural chemicals, the degraded fully of organic pollutions such as microorganism, improved the speed and the efficient of photocatalysis to degrade organic matter, thereby realized purification environment.This product almost is applied to the every field of national economy.As (1) room: can be widely used in surfaces such as wall, furniture, kitchen, toilet, floor, carpet, household electrical appliance, light fixture, artificial decoration product, play the purpose of good sterilization, sterilization, deodorizing, purification.(2) working environment: office, reception room, workshop, factory building.(3) public place: hospital, school, kindergarten, hotel, restaurant, guest room, public place of entertainment, station, common room etc.(4) vehicles: automobile, train, steamer, aircraft, traffic guardrail, guideboard, sound panel.(5) outdoor nonpolluting coating: skin, glass curtain wall, ceramic tile, billboard, illuminating lamp etc.Simultaneously also solve powder Nano titanium dioxide particulate secondary agglomeration problem, reached the nano particle controllable granularity that in solution, is uniformly dispersed.It is neutral that this transparency emulsion is, and can steady in a long-termly exist.In China's environmental pollution situation still very severe today, develop this nano composite photo-catalyst efficiently, existing theory significance, with practical value again.
Description of drawings
Fig. 1 is the mix TEM photo of samples of latex of the present invention
Fig. 2 is the comparison to the acid red dye degradation rate of emulsion of the present invention and other samples
Among the figure:
Sample 1: dopen Nano TiO of the present invention
2Transparent photo-catalytic emulsion
Sample 2: green angel's photocatalyst that Shanghai Sanrui Chemistry Co., Ltd produces
Sample 3: go up the clean photocatalyst of Kang Rui that the auspicious clean Environmental Protection Technology Co., Ltd in Haikang produces
Sample 4: commercially available nano titanium oxide white emulsion
The specific embodiment
Embodiment 1
(1) under the room temperature, measures the 33mL titanium tetrachloride, slowly splash in the distilled water of 100mL, obtain clear solution with graduated cylinder;
(2) with 4.33 the gram lanthanum nitrates and 4.08 the gram cerous sulfates and 1.16 the gram ammonium metavanadates be dissolved in the above-mentioned solution, be stirred to whole dissolvings;
(3) adding pure water again in above-mentioned solution is 1000ml until solution, adds 10% ammoniacal liquor then in this solution, and adjusting the pH value is 9, produces a large amount of faint yellow precipitations;
(4) with above-mentioned precipitation vacuum filtration, spend deionised water up to do not contain Cl with liquor argenti nitratis ophthalmicus check
-Till, obtain the TiO of the mol ratio 10% of doped metal ion and titanium
2Filter cake;
(5) add 2100 ml waters making beating at above-mentioned filter cake, shear 50 minutes with high-speed shearing machine after, place round-bottomed flask, add the hydrogen peroxide of 60ml15%, 8 ℃ of stirring reactions 6 hours, obtain faint yellow transparent complex solution;
(6) get the above-mentioned clear solution of 400g, add 8 gram D-D-sorbites, decompose complex compounds, obtain 2.1% nano-TiO that mixes lanthanum and cerium and vanadium simultaneously at 150 ℃ of heating reflux reaction 1h
2Transparent photo-catalytic emulsion.This liquid is placed at normal temperatures and was not also generated the precipitation variation in 1 year, and it is neutral that its pH value is approximately.
Embodiment 2
(1) with 4.33 the gram lanthanum nitrates and 4.08 the gram cerous sulfates and 1.16 the gram ammonium metavanadates be dissolved in the 250ml water, be stirred to whole dissolvings;
(2) under the room temperature, get the 110ml titanium tetrachloride with graduated cylinder, slowly splash in the above-mentioned solution with separatory funnel, obtain clear solution, adding pure water is 1000ml until solution;
(3) add 10% ammoniacal liquor in above-mentioned solution, adjusting the pH value is 9, produces a large amount of faint yellow precipitations, will precipitate vacuum filtration, spend deionised water up to not containing Cl with the liquor argenti nitratis ophthalmicus check
-Till, obtain the TiO of the mol ratio 3% of total doped metal ion and titanium
2Filter cake;
(4) add 1350 ml waters making beating at above-mentioned filter cake, shear 50 minutes with high-speed shearing machine after, place round-bottomed flask, add the hydrogen peroxide of 90ml 15%, 4 ℃ of stirring reactions 8 hours, obtain faint yellow transparent complex solution at last.
(5) get the above-mentioned clear solution of 400g, add 6 gram oleic acid, decompose complex compounds, just obtained about 10% nano-TiO that is mixed with lanthanum, cerium and vanadium simultaneously at last at 130 ℃ of heating reflux reaction 1.5h
2Transparent photo-catalytic emulsion.This liquid is placed at normal temperatures and was not also generated the precipitation variation in 1 year, and it is neutral that its pH value is approximately.
Embodiment 3
(1) with 8.66 the gram lanthanum nitrates and 8.16 the gram cerous sulfates and 2.32 the gram ammonium metavanadates be dissolved in the 500ml water, be stirred to whole dissolvings;
(2) under the room temperature, get the 110ml titanium tetrachloride with graduated cylinder, slowly splash in the above-mentioned solution with separatory funnel, obtain clear solution, adding pure water is 1000ml until solution;
(3) add 10% ammoniacal liquor in above-mentioned solution, adjusting the pH value is 8.5, produces a large amount of faint yellow precipitations, will precipitate vacuum filtration, spend deionised water up to not containing Cl with the liquor argenti nitratis ophthalmicus check
-Till, obtain the TiO of the mol ratio 6% of total doped metal ion and titanium
2Filter cake;
(4) add 675 ml waters making beating at above-mentioned filter cake, shear 50 minutes with high-speed shearing machine after, place round-bottomed flask, add the hydrogen peroxide of 90ml 15%, 4 ℃ of stirring reactions 8 hours, obtain faint yellow transparent complex solution at last.
(5) get the above-mentioned clear solution of 400g, add 6 gram oleic acid, decompose complex compounds, just obtained about 20% at last and be mixed with lanthanum and and the nano-TiO of vanadium simultaneously at 130 ℃ of heating reflux reaction 1.5h
2Transparent photo-catalytic emulsion.This liquid is placed at normal temperatures and was not also generated the precipitation variation in 1 year, and it is neutral that its pH value is approximately.
Emulsion of the present invention and other samples are to the comparison of acid red dye degradation rate:
The parallel acid bright red 3r solution that to get 4 parts of concentration be 50mg/L places beaker, every part of 10ml, at the lucifuge place with composite mixed nano-TiO of the present invention
2Green angel's photocatalyst that transparent photo-catalytic emulsion, Shanghai Sanrui Chemistry Co., Ltd produce, the clean photocatalyst of Kang Rui of going up the production of the auspicious clean Environmental Protection Technology Co., Ltd in Haikang and commercially available nano titanium oxide white emulsion are got 10ml respectively and are added in the above-mentioned beaker, add water to 200ml then, do the contrast experiment, behind the pH value with watery hydrochloric acid conditioned reaction system, dark place magnetic agitation 10-15min, make and reach absorption and desorb balance between emulsion and the organic dyestuff, sampling; Place outdoor platform sunshine place to carry out catalytic reaction then, sampling and testing at set intervals, on the UV-1200 ultraviolet-visible spectrophotometer its A-λ curve being carried out all band (200-800nm) scans, write down the absorbance and the concentration thereof of this dye solution maximum absorption wave strong point (506.5nm), calculate its degradation rate.The composite mixed nano-TiO of the present invention after the result shows 40 minutes
2The degradation rate of transparent photo-catalytic emulsion reaches more than 98%, the degradation rate of green angel's photocatalyst that Shanghai Sanrui Chemistry Co., Ltd produces has reached 90%, the clean photocatalyst degradation rate of Kang Rui that the auspicious clean Environmental Protection Technology Co., Ltd in last Haikang produces is 54%, and the degradation rate of commercially available nano titanium oxide white emulsion has only 35%, composite mixed as shown in Figure 4 nano-TiO
2The performance of transparent photo-catalytic emulsion is best.
Listed examples of the present invention is intended to further illustrate this composite metal ion doped nano-TiO
2The preparation method of transparent photo-catalytic emulsion, and protection scope of the present invention is not constituted any restriction.All can obtain composite metal ion doped nano-TiO with the embodiment of the invention
2Transparent photo-catalytic emulsion.
Claims (4)
1, composite metal ion doped nano-TiO
2The photocatalyst transparency emulsion is characterized in that: comprise following part by weight in this emulsion: nano-TiO
2And the slaine that contains lanthanum, cerium and vanadium totally 2.1～20%, tween, class of department, D-D-sorbite or OP class emulsifying agent 1-10%, water surplus.
2, composite metal ion doped nano-TiO according to claim 1
2The photocatalyst transparency emulsion is characterized in that: describedly contain the slaine of lanthanum, cerium and vanadium and the mol ratio of titanium is 3.0-10%.
3, composite metal ion doped nano-TiO according to claim 1 and 2
2The preparation method of photocatalyst transparency emulsion is characterized in that: this emulsion prepares according to following steps:
A, the composite metal ion doped titanium tetrachloride aqueous solution of preparation:
According to the mol ratio of doped metal ion and titanium is that slaine that the ratio of 3.0-10% will contain lanthanum, cerium and vanadium is dissolved in the 100mL water and makes saline solns, gets the 33mL titanium tetrachloride and slowly splashes in the saline solns with separatory funnel, and it is fully mixed;
Or: under the room temperature, will analyze pure titanium tetrachloride and slowly splash in the distilled water, and be mixed with 10～50% clear solution, be that the ratio of 3.0-10% adds the slaine that contains cerium and vanadium according to the mol ratio of doped metal ion and titanium, is stirred to whole dissolvings;
B, hydrolysis:
Get the aqueous solution of steps A, add pure water 300～2000ml again, the slow ammoniacal liquor of Dropwise 5～13% in this solution then, adjust pH is 8～9, makes TiO
2+And La
3+, Ce
3+And VO
3+Produce the composite oxides co-precipitation, then vacuum filtration, spend deionised water up to not containing Cl with the liquor argenti nitratis ophthalmicus check
-Till, obtain being mixed with the TiO of composite metal ion
2Filter cake;
C, complexing:
Above-mentioned filter cake is added 10-100 water making beating doubly, after 5～90 minutes, place round-bottomed flask with the high-speed shearing machine shearing, add the hydrogen peroxide of 10～100ml 15%, at 0～10 ℃ of stirring reaction 3-12 hour, obtain complex solution faint yellow or that yellowish-brown is transparent;
D, decomposition complex compound
Get the above-mentioned clear solution of 400ml, add D-D-sorbite, op-10 emulsifying agent, oleic acid or the tween of 0.8～10g, decompose complex compound, be mixed with the nano-TiO of the composition metal doping of lanthanum, cerium and vanadium simultaneously at 110～150 ℃ of heating, stirring and refluxing 0.5-2h
2Transparent photo-catalytic emulsion.
4, composite metal ion doped nano-TiO according to claim 3
2The preparation method of transparent photo-catalytic emulsion is characterized in that: step B doping adds the slaine that contains lanthanum, cerium and vanadium and comprises lanthanum nitrate and cerous sulfate and metavanadic acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711884B (en) * | 2009-04-29 | 2013-07-17 | 浙江吉利汽车研究院有限公司 | Purifying liquid, preparation method thereof and application thereof in purifying in-vehicle air |
| CN104209108A (en) * | 2014-06-09 | 2014-12-17 | 深圳市天得一环境科技有限公司 | Photocatalyst for degrading formaldehyde based on complexing stable dispersion, and preparation method and application thereof |
| CN104209109A (en) * | 2014-06-09 | 2014-12-17 | 深圳市天得一环境科技有限公司 | Photocatalyst for degrading nitrogen oxide based on complexing stable dispersion, and preparation method and application thereof |
| CN108479856A (en) * | 2018-03-23 | 2018-09-04 | 河北大学 | A kind of photocatalyst and preparation method thereof used under dim light or no light condition |
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2008
- 2008-10-22 CN CNA2008100795997A patent/CN101380568A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711884B (en) * | 2009-04-29 | 2013-07-17 | 浙江吉利汽车研究院有限公司 | Purifying liquid, preparation method thereof and application thereof in purifying in-vehicle air |
| CN104209108A (en) * | 2014-06-09 | 2014-12-17 | 深圳市天得一环境科技有限公司 | Photocatalyst for degrading formaldehyde based on complexing stable dispersion, and preparation method and application thereof |
| CN104209109A (en) * | 2014-06-09 | 2014-12-17 | 深圳市天得一环境科技有限公司 | Photocatalyst for degrading nitrogen oxide based on complexing stable dispersion, and preparation method and application thereof |
| CN108479856A (en) * | 2018-03-23 | 2018-09-04 | 河北大学 | A kind of photocatalyst and preparation method thereof used under dim light or no light condition |
| CN108479856B (en) * | 2018-03-23 | 2020-11-24 | 保定绿怡佳环保科技有限公司 | Photocatalyst used under weak light or no light condition and preparation method thereof |
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